WO2018194154A1 - 感光性樹脂組成物及びその硬化物 - Google Patents
感光性樹脂組成物及びその硬化物 Download PDFInfo
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- WO2018194154A1 WO2018194154A1 PCT/JP2018/016265 JP2018016265W WO2018194154A1 WO 2018194154 A1 WO2018194154 A1 WO 2018194154A1 JP 2018016265 W JP2018016265 W JP 2018016265W WO 2018194154 A1 WO2018194154 A1 WO 2018194154A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
Definitions
- the present invention includes MEMS (micro electro mechanical system) parts, micro machine parts, micro fluid parts, ⁇ -TAS (micro total analysis system) parts, ink jet printer parts, micro reactor parts, conductive layers, LIGA parts, micro injection molding. And high-resolution negative photosensitive resin compositions useful in the manufacture of molds and stamps for heat embossing, screens or stencils for micro printing applications, MEMS package parts, semiconductor package parts, BioMEMS and biophotonic devices, and printed wiring boards Related to things.
- the present invention further relates to a cured product of the negative photosensitive resin composition having a high elastic modulus at high temperatures and excellent adhesion to various substrates.
- Photoresistable resists have recently been widely used in semiconductor and MEMS / micromachine applications.
- photolithography is achieved by patterning exposure on a substrate and then developing with a developer to selectively remove exposed or non-exposed areas.
- Resist (photoresist) that can be processed by photolithography includes a positive type or a negative type, and an exposed part dissolves in a developing solution is a positive type, and an insoluble part is a negative type.
- Advanced electro-package applications and MEMS applications require not only the ability to form a uniform spin coating film, but also a high aspect ratio, a straight sidewall shape in a thick film, and high adhesion to a substrate.
- the aspect ratio is an important characteristic calculated by resist film thickness / pattern line width and showing the performance of photolithography.
- Photoresist polymerization initiators such as polyfunctional bisphenol A novolak type epoxy resin (trade name: EPON SU-8 resin, manufactured by Resolution Performance Products) and Dow Chemical's CYRACURE UVI-6974 as such photoresists
- a negative-type chemically amplified photoresist composition containing (this photocationic polymerization initiator is composed of a propylene carbonate solution of aromatic sulfonium hexafluoroantimonate). Since the photoresist composition has very low light absorption in the wavelength range of 350 to 450 nm, it is known as a photoresist composition that can be processed by thick film photolithography.
- a solid photoresist layer having a thickness of 100 ⁇ m or more can be formed by applying this photoresist composition on various substrates by a technique such as spin coating or curtain coating and then evaporating the solvent by baking. Further, photolithography can be performed by irradiating the solid photoresist layer with near-ultraviolet light through a photomask by various exposure methods such as contact exposure, proximity exposure or projection exposure. Subsequently, a negative image of a high-resolution photomask can be formed on the substrate by immersing in a developing solution and dissolving the non-exposed areas.
- the cured product When a cured product of photoresist is used as a part such as a semiconductor package, for example, when the process of resin-sealing the cured product of photoresist together with other parts is included in the manufacture of a semiconductor package, the cured product includes A high elastic modulus at high temperature is required to maintain the shape even during resin sealing.
- substrates such as MEMS parts, MEMS packages, and semiconductor packages are not limited to conventional silicon wafers, but various types of substrates such as silicon nitride and lithium tantalate. Etc. may be used. Therefore, it is required for the photoresist that the cured product has excellent adhesion to these substrates.
- Patent Document 1 discloses a photosensitive resin composition containing a photocationic polymerization initiator having a specific structure and a polyfunctional epoxy resin. In the examples of this document, it is described that the cured product of the photosensitive resin composition is excellent in adhesion to a silicon wafer. However, this document does not mention anything about the elastic modulus at high temperature and the adhesion to a substrate other than a silicon wafer.
- the present invention has been made in view of the circumstances as described above, and is excellent in resolution.
- the cured product maintains a high elastic modulus even at a high temperature, and has good adhesion to various substrates other than a silicon wafer.
- An object is to provide an excellent negative photosensitive resin composition.
- a negative photosensitive compound containing a compound having a triazine skeleton having a specific structure, a polyfunctional epoxy resin having a benzene skeleton and satisfying specific parameters, and a photocationic polymerization initiator.
- the present inventors have found that a functional resin composition can solve the above problems, and have completed the present invention.
- each R 1 independently represents an organic group. However, at least one of R 1 represents an organic group having a glycidyl group or an organic group having an oxetanyl group.
- a negative photosensitive resin composition containing the following epoxy resin and (C) a cationic photopolymerization initiator,
- the content of the compound represented by formula (1) with respect to the (B) epoxy resin is 1 to 50% by mass
- the (B) epoxy resin has the following conditions (i) and (ii): A negative photosensitive resin composition satisfying at least one of condition (i) a weight average molecular weight of 500 or more; and condition (ii) a softening point of 40 ° C. or more. [2].
- At least one of R 1 is Following formula (1-1) (In formula (1-1), R 2 represents an alkylene group having 1 to 8 carbon atoms), Following formula (1-2) (In the formula (1-2), R 3 represents an alkylene group having 1 to 8 carbon atoms, and R 4 represents an alkyl group having 1 to 6 carbon atoms), or the following formula (1-3)
- Any of R 1 is an organic group represented by the formula (1-1), an organic group represented by the formula (1-2), or an organic group represented by the formula (1-3) [2 ] Negative photosensitive resin composition of claim
- At least one of R 1 is represented by the following formula (1-4) (In formula (1-4), R 5 represents a hydrogen atom or a methyl group.)
- An epoxy equivalent having a benzene skeleton and two or more epoxy groups in one molecule is 500 g / eq.
- the following epoxy resin Following formula (2) (In the formula (2), each R independently represents a glycidyl group or a hydrogen atom, and at least two of the plural Rs are glycidyl groups.
- K represents an average value and is in the range of 0 to 30.
- Epoxy resin (B-2) represented by Following formula (4) (In formula (4), n and m represent average values, n is a real number in the range of 1 to 30, m is a real number in the range of 0.1 to 30, and R 9 and R 10 are Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group.) Following formula (5) (In the formula (5), q represents an average value and is a real number in the range of 1 to 30).
- An epoxy resin (B-5) which is a reaction product of a phenol derivative represented by formula (II) and an epihalohydrin, Reacting a polybasic acid anhydride with a reaction product of an epoxy compound having at least two epoxy groups in one molecule and a compound having at least one hydroxyl group and one carboxyl group in one molecule;
- Epoxy resin (B-6) obtained by Following formula (7) (In the formula (7), s represents an average value and is a real number in the range of 1 to 10) represented by the epoxy resin (B-7),
- r represents an average value and is a real number in the range of 0.1 to 6.
- the negative photosensitive resin composition according to any one of items [1] to [4] above
- a dry film resist comprising the negative photosensitive resin composition according to any one of [1] to [5] above. [7].
- a wafer level package comprising the cured product according to the above item [7].
- the negative photosensitive resin composition of the present invention is excellent in resolution and also has a high effect of controlling the generation of post-development residues.
- the cured product maintains a high elastic modulus even at high temperatures, and various substrates other than silicon wafers. Excellent adhesion to. Therefore, this negative photosensitive resin composition is suitably used for MEMS parts, micromachine parts, semiconductor package parts, and the like.
- the negative photosensitive resin composition of the present invention contains (A) a compound having a triazine ring represented by the formula (1) (hereinafter simply referred to as “component (A)”).
- component (A) a compound having a triazine ring represented by the formula (1)
- each R 1 independently represents an organic group.
- the organic group represented by R 1 in the formula (1) is not particularly limited as long as the desired properties of the resin composition are not inhibited.
- a hydroxyl group, an aldehyde group, a carboxy group, a nitro group, an amino group, a sulfo group, a functional group such as a sulfo group and a cyano group, a halogeno group such as a bromine atom, a chlorine atom, a fluorine atom, and an iodine atom, and these groups are substituted.
- a residue obtained by removing one hydrogen atom from an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, or a heterocyclic compound which may be included is also included in the category of the organic group represented by R 1 in the formula (1).
- At least one of R 1 in Formula (1) represents an organic group having a glycidyl group or an oxetanyl group. That is, the compound having a triazine ring represented by the formula (1) is a compound having at least one glycidyl group or oxetanyl group.
- the organic group having a glycidyl group or an oxetanyl group represented by R 1 in the formula (1) is not particularly limited as long as it has a glycidyl group or an oxetanyl group, but the above formulas (1-1), (1-2) Or an organic group represented by (1-3).
- R 2 represents an alkylene group having 1 to 8 carbon atoms.
- the alkylene group having 1 to 8 carbon atoms represented by R 2 in the formula (1-1) is not limited to a linear, branched or cyclic group as long as the carbon number is 1 to 8.
- the alkylene group represented by R 2 may have an alkyl group as a substituent. In the case of having an alkyl group as a substituent, the total number of carbon atoms of the alkylene group and the alkyl group may be 1 to 8.
- the alkylene group represented by Formula (1-1) preferably has 1 to 6 carbon atoms in the main chain.
- alkylene having 1 to 6 carbon atoms include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, isopropylene group, isobutylene group and isopentylene group. , Neopentylene group, isohexylene group, cyclohexylene group and the like. From the viewpoints of lithography properties, adhesiveness, and heat resistance of the obtained cured product, a methylene group, an ethylene group or an n-propylene group is preferable, and an n-propylene group is more preferable.
- R 3 represents an alkylene group having 1 to 8 carbon atoms
- R 4 represents an alkyl group having 1 to 6 carbon atoms.
- Preferred examples of the alkylene group having 1 to 8 carbon atoms represented by R 3 in the formula (1-2) include the same alkylene groups having 1 to 8 carbon atoms represented by R 2 in the formula (1-1). The same can be mentioned.
- the alkyl group having 1 to 6 carbon atoms represented by R 4 in the formula (1-2) is not limited to a linear, branched or cyclic group as long as the carbon number is 1 to 6.
- Examples of the alkyl group having 1 to 6 carbon atoms represented by R 4 in the formula (1-2) include a linear or branched alkyl group having 1 to 6 carbon atoms and a cyclic alkyl group having 5 or 6 carbon atoms (cyclopentyl). Group and cyclohexyl group).
- R 4 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
- R 4 is more preferably a linear alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.
- R 1 includes an organic group represented by the formula (1-1), (1-2) or (1-3) and an organic group represented by the formula (1-4). It is also preferable to use a compound having a group.
- R 5 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- (A) The compound represented by Formula (1) preferable as a component is described below.
- (A) component can be obtained as a commercial product.
- Specific examples thereof include TEPIC (above (ii)), TEPIC-VL (above (i)), TEPIC-PAS (a mixture of modified products of (ii) and (ii) above), TEPIC-G, and TEPIC-S.
- DA-MGIC above (vi)
- TOIC above (iii)) (made by Shikoku Kasei)
- an epoxy equivalent having a benzene skeleton and two or more epoxy groups in one molecule is 500 g / eq. It contains the following epoxy resin having a weight average molecular weight of 500 or more and / or a softening point of 40 ° C. or more (hereinafter simply referred to as “component (B)”).
- component (B) include long-chain bisphenol-type epoxy resins such as long-chain bisphenol A-type epoxy resins and long-chain bisphenol F-type epoxy resins, and phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene).
- the component (B) is an epoxy resin that satisfies the above conditions in terms of epoxy equivalent, weight average molecular weight, and softening point, and is not limited to these as long as it is a polyfunctional epoxy resin having a benzene ring.
- component (B) examples include KM-N-LCL, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-4400H, EPPN-201, EPPN-501, EPPN-502 , XD-1000, BREN-S, NER-7604, NER-7403, NER-1302, NER-7516, NC-3000H (all trade names, manufactured by Nippon Kayaku Co., Ltd.) and Epicoat 157S70 (trade names, Mitsubishi Chemical) Etc.).
- the epoxy resins (B-1) and (B-2) are preferable because the cured product has high chemical resistance, plasma resistance and transparency, and the cured product has low moisture absorption.
- (B-3), (B-4), (B-5), (B-6), (B-7), (B-8) and (B-9) are preferred.
- (B-1), (B-2) and (B-3) are more preferable, and (B-1), (B-2) and (B-3) are more preferably used as a mixture.
- the epoxy resin (B-5) is a reaction product of a phenol derivative represented by the above formula (6) and an epihalohydrin.
- a phenol derivative represented by the formula (6) and an epihalohydrin such as epichlorohydrin and epibromohydrin
- a solvent capable of dissolving them After adding alkalis such as sodium hydroxide to the mixed solution and raising the temperature to the reaction temperature to perform addition reaction and ring closure reaction, the reaction solution is repeatedly washed with water, separated and the aqueous layer removed, and finally from the oil layer. The method of distilling a solvent off is mentioned.
- epoxy resins (B-5) having different main components can be obtained depending on the use ratio of the phenol derivative represented by the formula (6) used in the synthesis reaction and epihalohydrin.
- an epoxy resin mainly composed of a trifunctional epoxy resin in which all of the three phenolic hydroxyl groups in the formula (6) are epoxidized (B-5) is obtained.
- the content of increases. As a method for obtaining such an epoxy resin (B-5) containing a multimeric epoxy resin as a main component, in addition to the method of controlling by the use ratio of the phenol derivative and the epihalohydrin, the epoxy resin once obtained ( Another example is a method in which B-5) is further reacted with a phenol derivative.
- the epoxy resin (B-5) obtained by this method is also included in the category of the epoxy resin (B-5) contained in the photosensitive resin of the present invention.
- the reaction of the phenol derivative represented by the formula (6) with epihalohydrin is usually 0.3 to 30 mol, preferably 1 to 20 mol, more preferably epihalohydrin with respect to 1 mol of phenol derivative (corresponding to 3 mol of hydroxyl group). Is carried out at a ratio of 3 to 15 mol.
- the epoxy resin (B-5) contained in the resin composition of the present invention is an epoxy resin obtained by the reaction of a phenol derivative represented by the formula (6) and an epihalohydrin.
- An epoxy resin (B-5) containing either an epoxy resin or a phenol derivative multimeric epoxy resin as a main component can be used.
- the epoxy resin (B-5) is excellent in solvent solubility and has a low softening point and is easy to handle.
- an epoxy resin of a phenol derivative monomer, an epoxy resin of a phenol derivative dimer (formula (6))
- An epoxy resin (B-5) containing as a main component any one of the above-mentioned epoxy resins is preferable.
- An epoxy resin (B-5) having a phenol derivative monomer epoxy resin or a phenol derivative dimer epoxy resin as a main component is more preferable.
- the epoxy resin represented by the formula (2) means an epoxy resin mainly composed of the epoxy resin represented by the formula (2) (the number k of repeating units is an average value). And a case where a subcomponent generated when the epoxy resin is produced, a high molecular weight body of the epoxy resin, or the like is included. The same applies to epoxy resins that have cited formulas other than formula (2).
- epoxy resin (B-1) represented by the formula (2) examples include KM-N-LCL (trade name, bisphenol A novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 195 to 210 g. / Eq., Softening point 78 to 86 ° C.), Epicoat 157 (trade name, bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 to 250 g / eq., Softening point 80 to 90 ° C.), EPON SU -8 (trade name, bisphenol A novolak type epoxy resin, manufactured by Resolution Performance Products, epoxy equivalent of 195 to 230 g / eq., Softening point of 80 to 90 ° C.) and the like.
- KM-N-LCL trade name, bisphenol A novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 195 to 210 g. / Eq., Softening point 78 to 86 ° C.
- epoxy resin (B-2) represented by the formula (3) examples include NC-3000 series (trade name, biphenyl-phenol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 270 to 300 g. / Eq., Softening point 55 to 75 ° C.).
- NC-3000 series is NC-3000H.
- epoxy resin (B-3) represented by the formula (4) examples include NER-7604 and NER-7403 (both trade names, bisphenol F type epoxy in which a part of the alcoholic hydroxyl group is epoxidized).
- Resin Nippon Kayaku Co., Ltd., epoxy equivalent 200 to 500 g / eq., Softening point 55 to 75 ° C.
- NER-1302 and NER-7516 both trade names, part of alcoholic hydroxyl groups were epoxidized
- Bisphenol A type epoxy resin Nippon Kayaku Co., Ltd., epoxy equivalent 200 to 500 g / eq., Softening point 55 to 75 ° C.
- Specific examples of the epoxy resin (B-4) represented by the formula (5) include EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 190 to 210 g / eq., Softening point 55 to 85 ° C).
- Specific examples of the epoxy resin (B-5), which is a reaction product of the phenol derivative represented by the formula (6) and epihalohydrin include NC-6300 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 230 To 235 g / eq., Softening point of 70 to 72 ° C.).
- Examples of the epoxy resin (B-6) include polycarboxylic acid epoxy compounds described in Japanese Patent No. 2698499. The epoxy equivalent and softening point can be variously adjusted depending on the type of epoxy resin used as a raw material of the epoxy resin (B-6) and the introduction rate of substituents to be introduced.
- epoxy resin (B-7) represented by the formula (7) examples include EPPN-201-L (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 180 to 200 g / eq., Softening point 65 To 78 ° C.).
- epoxy resin (B-8) represented by the formula (8) examples include EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalents 162 to 172 g / eq., Softening points 51 to 57).
- EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 163 to 175 g / eq., Softening point 57 to 63 ° C.)
- EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent) 158 to 178 g / eq., Softening point 60 to 72 ° C.
- Specific examples of the epoxy resin (B-9) represented by the formula (9) include XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 245 to 260 g / eq., Softening point 68 to 78). ° C).
- the epoxy equivalent of the component (B) contained in the negative photosensitive resin composition of the present invention is preferably 150 to 500, and more preferably 150 to 450.
- the weight average molecular weight of the component (B) contained in the negative photosensitive resin composition of the present invention is preferably 500 to 15000, and more preferably 500 to 9000.
- the softening point of the component (B) contained in the negative photosensitive resin composition of the present invention is preferably 40 to 120 ° C, and preferably 40 to 110 ° C, 55 to 120 ° C, or 55 ° C to 110 ° C. Is more preferable.
- the epoxy equivalent in this invention is the value measured by the method based on JISK7236.
- the weight average molecular weight in the present invention is a value of a weight average molecular weight calculated in terms of polystyrene based on the measurement result of gel permeation chromatography.
- the softening point in the present invention is a value measured by a method based on JIS K7234.
- the content of the component (A) is 1 to 50% by mass, preferably 2 to 30% by mass, and preferably 3 to 20% by mass with respect to the component (B). % Is more preferable.
- content of (A) component in the negative photosensitive resin composition of this invention is 1 thru
- the negative photosensitive resin composition of the present invention contains (C) a photocationic polymerization initiator (hereinafter simply referred to as “component (C)”).
- component (C) contained in the photosensitive resin composition of the present invention generates cations upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, and electron beams. Is a compound that can be a polymerization initiator.
- Examples of the component (C) include aromatic iodonium complex salts and aromatic sulfonium complex salts.
- aromatic iodonium complex salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, tricumyl iodonium tetrakis (Pentafluorophenyl) borate (Rhodia, trade name Rhodosyl PI2074), di (4-tert-butyl) iodonium tris (trifluoromethanesulfonyl) methanide (BASF, trade name CGI BBI-C1), and the like.
- aromatic sulfonium complex salt examples include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San Apro, trade name CPI-101A), thiophenyl diphenyl sulfonium tris (pentafluoroethyl) trifluorophosphate (manufactured by San Apro, Trade name CPI-210S), 4- ⁇ 4- (2-chlorobenzoyl) phenylthio ⁇ phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (trade name SP-172, manufactured by ADEKA), 4-thiophenyldiphenyl A mixture of aromatic sulfonium hexafluoroantimonate containing sulfonium hexafluoroantimonate (trade name CPI-6976, manufactured by ACETO Corporation USA) and triphenylsulfone Umtris
- an aromatic sulfonium complex salt having high vertical rectangular workability and high thermal stability is preferred in the photosensitive image forming step in the present invention.
- Particularly preferred is a mixture of nates, tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate.
- Component (C) may be used alone or in combination of two or more in the negative photosensitive resin composition of the present invention. Since the component (C) has an action of absorbing light, when it is used in a thick film (for example, 50 ⁇ m or more) and the component (C) is used in a large amount (for example, in an amount exceeding 15% by mass), However, when a small amount (for example, less than 3% by mass) is used, it is not easy to obtain a sufficient curing rate. In the case of a thin film, sufficient performance is exhibited by adding a small amount (for example, 1% by mass or more) of the component (C).
- the blending ratio of the component (C) in the photosensitive resin composition of the present invention is usually 0.1 to 10% by mass, preferably with respect to the total mass of the component (A) and the component (B). 0.5 to 5% by mass.
- the mixture ratio of (C) component in the photosensitive resin composition of this invention is 0.1 to 5 mass% with respect to the total mass of (A) component and (B) component, or It may be 0.5 to 10% by mass.
- the molar extinction coefficient of the component (C) at a wavelength of 300 to 380 nm is high, it is necessary to adjust to an appropriate blending amount according to the film thickness when using the photosensitive resin composition.
- a miscible (D) reactive epoxy monomer may be added to the negative photosensitive resin composition of the present invention in order to improve pattern performance.
- a reactive epoxy monomer (D) a glycidyl ether compound which is liquid at room temperature can be used.
- a glycidyl ether compound diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (manufactured by ADEKA Corporation, ED506), trimethylolpropane triglycidyl ether (manufactured by ADEKA Corporation) , ED505), trimethylolpropane triglycidyl ether (low chlorine type, manufactured by Nagase ChemteX Corporation, EX321L), pentaerythritol tetraglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether (produced by ADEKA Corporation, EP4088L), and the like. It is done. Furthermore, since these epoxy monomers generally have a high chlorine content, it is preferable to use those of low chlorine type that have undergone a low
- the reactive epoxy monomer component is used for the purpose of improving the reactivity of the resist and the physical properties of the cured film.
- the reactive epoxy monomer component is often in a liquid state, and when the component is in a liquid state, if the amount is more than 20% by mass based on the total amount of the photosensitive resin composition, the film after the solvent is removed becomes sticky. In some cases, mask sticking is likely to occur. From this point, when blending the monomer component, the blending ratio is preferably 10% by mass or less (and more than 0% by mass), particularly 7% by mass with respect to the total mass of the component (A) and the component (B). % Or less is preferred.
- a solvent may be added in order to lower the viscosity of the composition and improve the coating properties.
- organic solvents that are usually used in inks, paints, and the like, and can dissolve each constituent of the photosensitive resin composition can be used without any particular limitation.
- Specific examples of the solvent include ketones such as acetone, ethyl methyl ketone, cyclohexanone and cyclopentanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether and dipropylene glycol.
- Glycol ethers such as diethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, esters such as propylene glycol monomethyl ether acetate and ⁇ -butyrolactone, alcohols such as methanol, ethanol, cellosolve and methyl cellosolve, octane and Examples include aliphatic hydrocarbons such as decane, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. .
- solvents can be used alone or in admixture of two or more.
- the solvent component is added for the purpose of adjusting the film thickness and coating property when applied to the substrate.
- the amount of the solvent used to properly maintain the solubility of the main component, the volatility of the component, the liquid viscosity of the composition, etc. is preferably 95% by mass or less in the negative photosensitive resin composition, more preferably 10 to 90% by mass.
- a miscible adhesion imparting agent may be used for the purpose of improving the adhesion of the composition to the substrate.
- a coupling agent such as a silane coupling agent or a titanium coupling agent can be used.
- a silane coupling agent is used.
- silane coupling agents include 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and the like.
- adhesiveness imparting agents can be used alone or in combination of two or more. Since the adhesion-imparting agent is unreactive with the main component, components other than those that act at the substrate interface will be present as residual components after curing. Accordingly, when a large amount of the adhesion-imparting agent is used, physical properties may be deteriorated. Depending on the substrate, it is appropriate to use it within a range that does not cause a decrease in physical properties, since the effect is exhibited even in a small amount.
- the use ratio of the adhesion-imparting agent is preferably 15% by mass or less, more preferably 5% by mass or less in the negative photosensitive resin composition.
- a sensitizer may be used for further absorbing ultraviolet light and supplying the absorbed light energy to the photocationic polymerization initiator.
- the sensitizer for example, thioxanthones and anthracene compounds having an alkoxy group at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives) are preferable.
- alkoxy group C1-C4 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, are mentioned, for example.
- the 9,10-dialkoxyanthracene derivative may further have a substituent.
- substituents examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group, an alkyl sulfonate group, and an alkyl carboxylate.
- An ester group etc. are mentioned.
- alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester include alkyl having 1 to 4 carbon atoms such as methyl, ethyl, and propyl.
- the substitution position of these substituents is preferably the 2-position.
- thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and 2-isopropylthioxanthone.
- 2,4-diethylthioxanthone trade name Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.
- 2-isopropylthioxanthone is preferred.
- Examples of the 9,10-dialkoxyanthracene derivative include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dimethoxy-2.
- sensitizers can be used alone or in combination of two or more. Most preferred is the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene. Since the sensitizer component exhibits an effect in a small amount, its use ratio is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the component (C).
- trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxy are used when it is necessary to reduce the adverse effects caused by the ions derived from the component (C).
- Alkoxyaluminum such as aluminum and trisbutoxyaluminum
- Phenoxyaluminum such as trisphenoxyaluminum and trisparamethylphenoxyaluminum
- Trisacetoxyaluminum Trisstearatoaluminum, Trisbutyrataluminum, Trispropionatoaluminum
- Trisacetylacetonatoaluminum Tris Trifluoroacetylacetonatoaluminum
- trisethylacetoacetatoaluminum, diacetylacetonatodipivaloyl Ion catcher such as shelf preparative aluminum and diisopropoxy (ethylacetoacetato) an organoaluminum compound such as aluminum may be added.
- These ion catchers can be used alone or in combination of two or more.
- the compounding quantity may be 10 mass% or less with respect to the total solid (all components except a solvent) of the negative photosensitive resin composition of this invention
- thermoplastic resin examples include polyethersulfone, polystyrene, and polycarbonate.
- colorant examples include phthalocyanine blue, phthalocyanine green, iodin green, crystal violet, titanium oxide, carbon black, naphthalene black and the like.
- thickener examples include olben, benton, montmorillonite and the like.
- antifoaming agent examples include silicone-based, fluorine-based and polymer-based antifoaming agents.
- Examples of the negative photosensitive resin composition of the present invention include barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Fillers can be added. The addition amount of the inorganic filler may be 60% by mass or less in the photosensitive composition of the present invention.
- the negative photosensitive resin composition of the present invention is composed of the essential components (A), (B) and (C), and, if necessary, a solvent, various additives and the like. It can be prepared simply by mixing and stirring by the method. You may disperse
- the negative photosensitive resin composition of the present invention is preferably used in the form of a solution to which a solvent is added.
- a solvent for example, a metal substrate such as silicon, aluminum or copper, a ceramic substrate such as lithium tantalate, glass, silicon oxide or silicon nitride.
- the negative photosensitive resin composition of the present invention can be applied to a thickness of 0.1 to 1000 ⁇ m using a spin coater on a substrate such as polyimide or polyethylene terephthalate. Next, after removing the solvent under a heating condition of 60 to 130 ° C.
- an organic solvent such as ⁇ -butyrolactone, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a mixed solution of the organic solvent and water can be used.
- a paddle type, spray type, shower type, or other developing device may be used. You may perform ultrasonic irradiation as needed.
- aluminum is mentioned as a preferable metal substrate in using the negative photosensitive resin composition of this invention.
- the negative photosensitive resin composition of the present invention is applied to the base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then dried at 45 to 100 ° C.
- a dry film resist can be obtained by drying in an oven and removing a predetermined amount of solvent, or by laminating a cover film or the like as necessary. At this time, the thickness of the resist on the base film can be adjusted to 2 to 100 ⁇ m.
- films, such as polyester, a polypropylene, polyethylene, TAC, a polyimide, are used, for example.
- a film subjected to a release treatment with a silicone-type release treatment agent, a non-silicone-type release treatment agent, or the like may be used as necessary.
- the cover film is peeled off, transferred to a substrate at a temperature of 40 to 100 ° C. under a pressure of 0.05 to 2 MPa by a hand roll or a laminator, etc., and the negative photosensitive resist dissolved in the solvent.
- the exposure, post-exposure bake, development, and heat treatment may be performed as in the case of the conductive resin composition.
- the negative photosensitive resin composition is supplied as a dry film as described above, the steps of coating on the support and drying can be omitted. Thereby, the cured product pattern using the negative photosensitive resin composition of the present invention can be more easily formed.
- a MEMS package or a semiconductor package When used as a MEMS package or a semiconductor package, it can be used by covering the MEMS or semiconductor device with the negative photosensitive resin composition of the present invention or producing a hollow structure for the MEMS or semiconductor device.
- a substrate for MEMS and semiconductor packages a thin metal film of aluminum, gold, copper, chromium, titanium or the like is formed on a silicon wafer of various shapes by sputtering or vapor deposition to a thickness of 10 to 5000 mm, and etched by an etching method or the like. A substrate or the like obtained by finely processing the metal is used.
- silicon oxide or silicon nitride may be formed as an inorganic protective film with a thickness of 10 to 10,000 mm.
- the partition wall is formed on the substrate by the above-described method, and further, the dry film is laminated by the above-described method and patterned so as to be a lid on the partition wall.
- a hollow package structure can be produced.
- a MEMS package part and a semiconductor package part satisfying various characteristics can be obtained by performing heat treatment at 130 to 200 ° C. for 10 to 120 minutes as necessary.
- the “package” is a sealing method used to block the intrusion of gas or liquid from the outside, or a product thereof, in order to maintain the stability of the substrate, wiring, elements, and the like.
- “Package” referred to in this specification refers to a device having a driving unit such as a MEMS, a hollow package for packaging a vibrator such as a SAW device, a deterioration of a semiconductor substrate, a printed wiring board, wiring, or the like. Represents surface protection, resin sealing, and the like performed to prevent the above.
- the “wafer level package” referred to in the present specification represents a package method or a product thereof, in which a protective film, terminals, wiring processing, and a package are performed in a wafer state, and then cut into chips.
- the negative photosensitive resin composition of the present invention has excellent image resolution and high elastic modulus at high temperature, and exhibits excellent effects such as excellent adhesion to various substrates other than silicon wafers. Therefore, this negative photosensitive resin composition is, for example, a MEMS (micro electro mechanical system) part, a micro machine part, a micro fluid part, a ⁇ -TAS (micro total analysis system) part, an ink jet printer part, a micro reactor part, For production of conductive layers, LIGA parts, molds and stamps for micro injection molding and heat embossing, screens or stencils for micro printing applications, MEMS package parts, semiconductor package parts, BioMEMS and biophotonic devices, and printed wiring boards Used. Especially, it is useful in MEMS package parts and semiconductor package parts.
- a compound having a triazine ring as component (A) contained in a negative photosensitive resin composition (mixture of plural components) as a product, a benzene skeleton and two or more epoxy groups in one molecule of component (B) The structural identification and content ratio analysis of each component of the epoxy resin having (C) photocationic polymerization initiator and the analysis results of the samples by 1 H-NMR, 13 C-NMR, LC-MS measurement, etc. Can be done by comparing and contrasting. Moreover, if the structure of the epoxy resin of component (B) is clarified, its epoxy equivalent, weight average molecular weight and softening point can be obtained.
- Examples 1 to 4, Comparative Example 1 and Comparative Example 2 Preparation of photosensitive resin composition
- (A) a compound having a triazine ring, (B) an epoxy resin, (C) a photocationic polymerization initiator and other components are heated at 60 ° C. in a flask with a stirrer. The mixture was stirred and mixed for 2 hours to obtain a negative photosensitive resin composition for comparison with the present invention.
- the substrate was subjected to post-exposure baking (PEB) at 95 ° C. for 6 minutes using a hot plate, and then developed at 23 ° C. for 6 minutes by an immersion method using propylene glycol monomethyl ether acetate. Then, a hard baking process was performed for 60 minutes in an oven (in a nitrogen atmosphere) at 200 ° C. to obtain a pattern of a negative photosensitive resin composition cured on a Si wafer substrate and a substrate on which SiN was formed.
- PEB post-exposure baking
- PEB post-exposure baking
- a hard baking process was performed for 60 minutes in an oven (in a nitrogen atmosphere) at 200 ° C. to obtain a pattern of a negative photosensitive resin composition cured on a Si wafer substrate and a substrate on which SiN was formed.
- the adhesion force is the shear strength (shear strength) at the time when the pattern is peeled off the substrate by applying force from the side surface of the pattern using a shear tool.
- a higher value is preferable because the adhesion between the substrate and the resin composition is higher.
- a block-like resist pattern of 100 ⁇ m ⁇ 100 ⁇ m (film thickness is 20 ⁇ m) is formed on each substrate with the optimum exposure amount obtained above, and a bonding tester (manufactured by Reska Co., Ltd.) is used. The breaking load was measured when a load was applied from the lateral direction to a position 3 ⁇ m high from the substrate at a speed of 50 ⁇ m / sec. The results are shown in Table 1 below.
- a cured product of the negative photosensitive resin composition is prepared with the optimum exposure amount obtained in the sensitivity evaluation of the negative photosensitive resin composition, and a DMA measuring apparatus (RSA-G2 manufactured by TA Instruments) is used.
- the elastic modulus at 175 ° C. was measured under the conditions of tensile mode, 1 Hz, and ramp rate of 3 ° C./sec. The results are shown in Table 1 below.
- (A-1) to (G) are as follows.
- R 1 is an organic group
- R 2 is represented by the formula methylene group (1-1)
- the R 1 remaining Two are compounds of an organic group represented by the formula (1-4) wherein R 5 is a hydrogen atom
- B-1 Trade name KM-N-LCL Nippon Kayaku Co., Ltd., epoxy equivalent 210 g / eq.
- Softening point 85 ° C., weight average molecular weight 8000, average number of repetitions k 4 (epoxy resin represented by formula (2))
- B-2) Trade name NC-3000H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 285 g / eq.
- Weight average molecular weight 2900 (C-1): Photoacid generator (tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate, trade name PAG290, manufactured by BASF) )
- D-1 Trade name EX-321L, manufactured by Nagase ChemteX Corporation, epoxy equivalent 140 g / eq.
- (Trimethylolpropane triglycidyl ether) (D-2): Trade name EP-4088L, manufactured by ADEKA Corporation, epoxy equivalent 165 g / eq.
- E Sicyclopentadiene dimethanol diglycidyl ether
- F Silane coupling agent (trade name S-510, manufactured by Chisso Corporation)
- F Leveling agent (Brand name Footage 222F, manufactured by Neos Co., Ltd.)
- G Solvent (ethylene glycol dimethyl ether, trade name Highsolve MMM, manufactured by Toho Chemical Industry Co., Ltd.)
- the negative photosensitive resin compositions (Examples 1 to 4) of the present invention have a higher elastic modulus at 175 ° C. than the negative photosensitive resin compositions of Comparative Examples 1 and 2, and It is clear that the adhesion to Si and SiN is also high (at least comparable).
- the post-development residue here refers to the undissolved residue of the negative photosensitive resin composition that remains in the unexposed portion after development and must be removed by the development process.
- the solvent was dried under conditions of 2 minutes to provide each negative photosensitive resin composition layer (dry film) having a thickness of 20 ⁇ m.
- a sample for evaluation obtained by pasting a PET film on each negative photosensitive resin composition layer obtained above at 60 ° C. and 0.3 MPa using a laminator was obtained at a temperature of 40 ° C. For 2 weeks in an atmosphere of 90% humidity.
- the negative photosensitive resin composition layer exposed by peeling the PET film on one side from the sample for evaluation obtained above is placed on a silicon (Si) wafer substrate under the conditions of 60 ° C. and 0.3 MPa using a laminator. After bonding, heat treatment was performed on a hot plate at 65 ° C. for 5 minutes. Next, development is performed on a silicon (Si) wafer substrate with a negative photosensitive resin composition layer obtained by peeling off the remaining one-side PET film, using propylene glycol monomethyl ether acetate by a dipping method at 23 ° C. for 6 minutes. Processed.
- the photosensitive resin composition according to the present invention can form a pattern with high adhesion to various substrates and has a high effect of controlling the generation of residues after development. Suitable for the field.
- the photosensitive resin composition of the present invention has an elastic modulus at high temperature and adhesion to various materials, which is advantageous for forming a cavity during molding.
- the final product can be made thinner, and it can be expected to increase the degree of freedom of design.
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Abstract
Description
[1].
(A)下記式(1)
(式(1)中、R1はそれぞれ独立に有機基を表す。但し、R1の少なくとも一つはグリシジル基を有する有機基又はオキセタニル基を有する有機基を表す。)
で表されるトリアジン環を有する化合物、
(B)一分子中にベンゼン骨格と二つ以上のエポキシ基を有するエポキシ当量が500g/eq.以下のエポキシ樹脂、及び
(C)光カチオン重合開始剤を含有するネガ型感光性樹脂組成物であって、
該(B)エポキシ樹脂に対する該(A)式(1)で表される化合物の含有量が1乃至50質量%であり、且つ、
該(B)エポキシ樹脂が下記条件(i)及び(ii):
条件(i)重量平均分子量が500以上であること;及び
条件(ii)軟化点が40℃以上であること
の少なくとも一方を満たす、ネガ型感光性樹脂組成物。
[2].
R1の少なくとも一つが、
下記式(1-1)
(式(1-1)中、R2は炭素数1乃至8のアルキレン基を表す。)、
下記式(1-2)
(式(1-2)中、R3は炭素数1乃至8のアルキレン基を表し、R4は炭素数1乃至6のアルキル基を表す。)、又は
下記式(1-3)
で表される有機基である、上記[1]項に記載のネガ型感光性樹脂組成物。
[3].
R1のいずれもが式(1-1)で表される有機基、式(1-2)で表される有機基又は式(1-3)で表される有機基である、上記[2]項に記載のネガ型感光性樹脂組成物。
[4].
R1の少なくとも一つが、下記式(1-4)
(式(1-4)中、R5は水素原子又はメチル基を表す。)
で表される有機基である、上記[2]項に記載のネガ型感光性樹脂組成物。
[5].
(B)一分子中にベンゼン骨格と二つ以上のエポキシ基を有するエポキシ当量が500g/eq.以下のエポキシ樹脂が、
下記式(2)
(式(2)中、Rはそれぞれ独立にグリシジル基又は水素原子を示し、複数存在するRのうちの少なくとも2つはグリシジル基である。kは平均値を示し、0乃至30の範囲にある実数である。)で表されるエポキシ樹脂(B-1)、
下記式(3)
(式(3)中、R6、R7及びR8は、それぞれ独立に水素原子又は炭素数1乃至4のアルキル基を示す。pは平均値を示し1乃至30の範囲にある実数である。)で表されるエポキシ樹脂(B-2)、
下記式(4)
(式(4)中、n及びmは平均値を示し、nは1乃至30の範囲にある実数であり、mは0.1乃至30の範囲にある実数であり、R9及びR10は、それぞれ独立に水素原子、炭素数1乃至4のアルキル基又はトリフルオロメチル基を示す。)で表されるエポキシ樹脂(B-3)、
下記式(5)
(式(5)中、qは平均値を示し、1乃至30の範囲にある実数である。)で表されるエポキシ樹脂(B-4)、
下記式(6)
で表されるフェノール誘導体と、エピハロヒドリンとの反応物であるエポキシ樹脂(B-5)、
1分子中に少なくとも2個以上のエポキシ基を有するエポキシ化合物と1分子中に少なくとも1個以上の水酸基と1個のカルボキシル基を有する化合物との反応物に、多塩基酸無水物を反応させることにより得られるエポキシ樹脂(B-6)、
下記式(7)
(式(7)中、sは平均値を示し、1乃至10の範囲にある実数である。)で表されるエポキシ樹脂(B-7)、
下記式(8)
(式(8)中、tは平均値を示し、0.1乃至5の範囲にある実数である。)で表されるエポキシ樹脂(B-8)、及び
下記式(9)
(式(9)中、rは平均値を示し、0.1乃至6の範囲にある実数である。)で表されるエポキシ樹脂(B-9)からなる群から選択される1種類又は2種類以上である、
上記[1]~[4]項のいずれか一項に記載のネガ型感光性樹脂組成物。
[6].
上記[1]~[5]項のいずれか一項に記載のネガ型感光性樹脂組成物を含むドライフィルムレジスト。
[7].
上記[1]~[5]項のいずれか一項に記載のネガ型感光性樹脂組成物又は上記[6]項に記載のドライフィルムレジストの硬化物。
[8].
上記[7]項に記載の硬化物を含むウエハーレベルパッケージ。
[9].
基板と被着体との接着層であって、上記[7]項に記載の硬化物を含む接着層。
本発明のネガ型感光性樹脂組成物は、(A)前記式(1)で表されるトリアジン環を有する化合物(以下、単に「(A)成分」と記載する)を含有する。
式(1)中、R1はそれぞれ独立に有機基を表す。式(1)のR1が表す有機基は、本樹脂組成物の所望の特性を阻害するものでない限り、特に限定されない。例えば、ヒドロキシ基、アルデヒド基、カルボキシ基、ニトロ基、アミノ基、スルホ基及びシアノ基等の官能基、臭素原子、塩素原子、弗素原子、沃素原子等のハロゲノ基、これらの基で置換されていてもよい脂肪族炭化水素化合物、芳香族炭化水素化合物又は複素環化合物から水素原子を一つ除いた残基も、式(1)のR1が表す有機基の範疇に含まれる。
但し、式(1)中のR1の少なくとも一つはグリシジル基を有する有機基又はオキセタニル基を有する有機基を表す。即ち、式(1)で表されるトリアジン環を有する化合物は、少なくとも一つのグリシジル基又はオキセタニル基を有する化合物である。
式(1)中のR1が表すグリシジル基又はオキセタニル基を有する有機基は、グリシジル基又はオキセタニル基を有してさえすれば特に限定されないが、上記式(1-1)、(1-2)又は(1-3)で表される有機基であることが好ましい。
式(1-1)のR2が表す炭素数1乃至8のアルキレン基は、炭素数が1乃至8であれば直鎖状、分岐鎖状又は環状の何れにも限定されない。R2が表すアルキレン基はアルキル基を置換基として有していてもよい。置換基としてアルキル基を有している場合はアルキレン基の炭素数とアルキル基の炭素数の合計が1乃至8であればよい。
式(1-1)が表すアルキレン基の主鎖の炭素数は1乃至6であることが好ましい。該炭素数1乃至6のアルキレンの具体例としては、メチレン基、エチレン基、n-プロピレン基、n-ブチレン基、n-ペンチレン基、n-へキシレン基、イソプロピレン基、イソブチレン基、イソペンチレン基、ネオペンチレン基、イソヘキシレン基、シクロヘキシレン基等が挙げられる。得られる硬化物のリソグラフィー性、接着性、耐熱性の観点から、メチレン基、エチレン基又はn-プロピレン基が好ましく、n-プロピレン基がより好ましい。
式(1-2)のR3が表す炭素数1乃至8のアルキレン基としては、式(1-1)のR2が表す炭素数1乃至8のアルキレン基と同じものが挙げられ、好ましいものも同じものが挙げられる。
式(1-2)のR4が表す炭素数1乃至6のアルキル基は、炭素数が1乃至6であれば直鎖状、分岐鎖状又は環状の何れにも限定されない。
式(1-2)のR4が表す炭素数1乃至6のアルキル基としては、炭素数1乃至6の直鎖又は分岐鎖のアルキル基、及び炭素数5又は6の環状のアルキル基(シクロペンチル基及びシクロヘキシル基)が挙げられる。R4は、炭素数1乃至6の直鎖又は分岐鎖のアルキル基であることが好ましい。R4は、直鎖の炭素数1乃至4のアルキル基であることがより好ましく、メチル基又はエチル基であることが更に好ましく、エチル基であることが特に好ましい。
(i)R1の全てが、R2がn-プロピレン基の式(1-1)で表される有機基の化合物。
(ii)R1の全てが、R2がメチレン基の式(1-1)で表される有機基の化合物。
(iii)R1の全てが、R3がメチレン基であってR4がエチル基の式(1-2)で表される有機基の化合物。
(iv)R1の全てが、式(1-3)で表される有機基の化合物。
(v)R1の一つが、R2がメチレン基の式(1-1)で表される有機基であって、R1の残りの二つが、R5が水素原子の式(1-4)で表される有機基の化合物。
(vi)R1の二つが、R2がメチレン基の式(1-1)で表される有機基であって、R1の残りの一つが、R5が水素原子の式(1-4)で表される有機基の化合物。
この様な(B)成分の具体例としては、KM-N-LCL、EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-4400H、EPPN-201、EPPN-501、EPPN-502、XD-1000、BREN-S、NER-7604、NER-7403、NER-1302、NER-7516、NC-3000H(いずれも商品名、日本化薬株式会社製)及びエピコート157S70(商品名、三菱化学株式会社製)等が挙げられる。
エポキシ樹脂(B-5)の一般的な合成方法としては、例えば、式(6)で表されるフェノール誘導体及びエピハロヒドリン(エピクロロヒドリンやエピブロモヒドリン等)を溶解し得る溶剤に溶解した混合溶液に、水酸化ナトリウム等のアルカリ類を添加し、反応温度まで昇温して付加反応及び閉環反応を行った後、反応液の水洗、分離及び水層の除去を繰り返し、最後に油層から溶剤を留去する方法が挙げられる。
前記の合成反応に用いる式(6)で表されるフェノール誘導体とエピハロヒドリンとの使用比率によって、主成分の異なるエポキシ樹脂(B-5)が得られることが知られている。例えば、フェノール誘導体のフェノール性水酸基に対して過剰量のエピハロヒドリンを用いた場合、式(6)中の3つのフェノール性水酸基の全てがエポキシ化された3官能のエポキシ樹脂を主成分とするエポキシ樹脂(B-5)が得られる。フェノール性水酸基に対するエピハロヒドリンの使用量が少なくなるのに伴い、複数のフェノール誘導体のフェノール性水酸基がエピハロヒドリンを介して結合し、残りのフェノー性水酸基がエポキシ化された重量平均分子量の大きい多官能エポキシ樹脂の含有率が増加する。
この様な多量体のエポキシ樹脂を主成分とするエポキシ樹脂(B-5)を得る方法としては、前記のフェノール誘導体とエピハロヒドリンの使用比率で制御する方法の他に、いったん得られたエポキシ樹脂(B-5)に更にフェノール誘導体を反応させる方法も挙げられる。該方法で得られたエポキシ樹脂(B-5)も本発明の感光性樹脂の含有するエポキシ樹脂(B-5)の範疇に含まれる。
式(6)で表されるフェノール誘導体とエピハロヒドリンとの反応は、フェノール誘導体1モル(水酸基3モル相当)に対して、エピハロヒドリンを通常0.3乃至30モル、好ましくは1乃至20モル、より好ましくは3乃至15モルの割合で用いて行われる。
前記式(3)で表されるエポキシ樹脂(B-2)の具体例としては、NC-3000シリーズ(商品名、ビフェニル-フェノールノボラック型エポキシ樹脂、日本化薬株式会社製、エポキシ当量270乃至300g/eq.、軟化点55乃至75℃)が挙げられる。NC-3000シリーズの好ましい例として、NC-3000Hが挙げられる。
前記式(5)で表されるエポキシ樹脂(B-4)の具体例としては、EOCN-1020(商品名、日本化薬株式会社製、エポキシ当量190乃至210g/eq.、軟化点55乃至85℃)が挙げられる。
前記式(6)で表されるフェノール誘導体と、エピハロヒドリンとの反応物であるエポキシ樹脂(B-5)の具体例としては、NC-6300(商品名、日本化薬株式会社製、エポキシ当量230乃至235g/eq.、軟化点70乃至72℃)が挙げられる。
エポキシ樹脂(B-6)としては、特許第2698499号公報に製法が記載されたポリカルボン酸エポキシ化合物が挙げられる。そのエポキシ当量及び軟化点は、エポキシ樹脂(B-6)の原料として用いるエポキシ樹脂の種類や導入する置換基の導入率によって種々調整が可能である。
前記式(8)で表されるエポキシ樹脂(B-8)の具体例としては、EPPN-501H(商品名、日本化薬株式会社製、エポキシ当量162乃至172g/eq.、軟化点51乃至57℃)、EPPN-501HY(商品名、日本化薬株式会社製、エポキシ当量163乃至175g/eq.、軟化点57乃至63℃)、EPPN-502H(商品名、日本化薬株式会社製、エポキシ当量158乃至178g/eq.、軟化点60乃至72℃)が挙げられる。
前記式(9)で表されるエポキシ樹脂(B-9)の具体例としては、XD-1000(商品名、日本化薬株式会社製、エポキシ当量245乃至260g/eq.、軟化点68乃至78℃)が挙げられる。
本発明のネガ型感光性樹脂組成物が含有する(B)成分の重量平均分子量は500乃至15000であることが好ましく、500乃至9000であることがより好ましい。
本発明のネガ型感光性樹脂組成物が含有する(B)成分の軟化点は40乃至120℃であることが好ましく、40乃至110℃、55乃至120℃、または55℃乃至110℃であることがより好ましい。
なお、本発明におけるエポキシ当量とは、JIS K7236に準拠した方法で測定した値である。本発明における重量平均分子量とは、ゲルパーミエーションクロマトグラフィーの測定結果に基づいてポリスチレン換算で算出した重量平均分子量の値である。本発明における軟化点とは、JIS K7234に準拠した方法で測定した値である。
また、別の態様において、本発明のネガ型感光性樹脂組成物における(A)成分の含有量は、(B)成分に対して1乃至30質量%、1乃至20質量%、2乃至50質量%、2乃至20質量%、3乃至50質量%、または3乃至30質量%であることが好ましい。
本発明の感光性樹脂組成物が含有する(C)成分は、紫外線、遠紫外線、KrFやArFなどのエキシマレーザー、X線および電子線などの放射線の照射を受けてカチオンを発生し、そのカチオンが重合開始剤となりうる化合物である。
(C)成分としては、芳香族ヨードニウム錯塩や芳香族スルホニウム錯塩を挙げることができる。
芳香族ヨードニウム錯塩の具体例としては、ジフェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ(4-ノニルフェニル)ヨードニウムヘキサフルオロホスフェート、トリルクミルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート(ローディア社製、商品名 ロードシルPI2074)、ジ(4-ターシャリブチル)ヨードニウムトリス(トリフルオロメタンスルホニル)メタニド(BASF社製、商品名 CGI BBI-C1)等が挙げられる。
芳香族スルホニウム錯塩の具体例としては、4-チオフェニルジフェニルスルホニウムヘキサフルオロアンチモネート(サンアプロ社製、商品名 CPI-101A)、チオフェニルジフェニルスルホニウムトリス(ペンタフルオロエチル)トリフルオロホスフェート(サンアプロ社製、商品名 CPI-210S)、4-{4-(2-クロロベンゾイル)フェニルチオ}フェニルビス(4-フルオロフェニル)スルホニウムヘキサフルオロアンチモネート(ADEKA社製、商品名 SP-172)、4-チオフェニルジフェニルスルホニウムヘキサフルオロアンチモネートを含有する芳香族スルホニウムヘキサフルオロアンチモネートの混合物(ACETO Corporate USA製、商品名 CPI-6976)及びトリフェニルスルホニウムトリス(トリフルオロメタンスルホニル)メタニド(BASF社製、商品名 CGI TPS-C1)、トリス[4-(4-アセチルフェニル)スルホニルフェニル]スルホニウムトリス(トリフルオロメチルスルホニル)メチド(BASF社製、商品名 GSID 26-1)、トリス[4-(4-アセチルフェニル)スルホニルフェニル]スルホニウムテトラキス(2,3,4,5,6-ペンタフルオロフェニル)ボレート(BASF社製、商品名 イルガキュアPAG290)等が挙げられる。これらの(C)成分のうち、本発明では感光画像形成工程において、垂直矩形加工性が高く、熱安定性が高い、芳香族スルホニウム錯塩が好ましい。これらの中でも、4-{4-(2-クロロベンゾイル)フェニルチオ}フェニルビス(4-フルオロフェニル)スルホニウムヘキサフルオロアンチモネート、4-チオフェニルジフェニルスルホニウムヘキサフルオロアンチモネートを含有する芳香族スルホニウムヘキサフルオロアンチモネートの混合物、トリス[4-(4-アセチルフェニル)スルホニルフェニル]スルホニウムテトラキス(2,3,4,5,6-ペンタフルオロフェニル)ボレートが特に好ましい。
密着性付与剤は、主成分とは未反応性のものであるため、基材界面で作用する成分以外は硬化後に残存成分として存在することになる。従って、密着性付与剤を多量に使用すると物性低下を生じることがある。基材によっては、少量でも効果を発揮する点から、物性低下を生じない範囲内での使用が適当である。密着性付与剤の使用割合は、ネガ型感光性樹脂組成物中に15質量%以下が好ましく、より好ましくは5質量%以下である。
表1に記載の配合量(単位は質量部)に従い、(A)トリアジン環を有する化合物、(B)エポキシ樹脂、(C)光カチオン重合開始剤および他の成分を、攪拌機付きフラスコで60℃、2時間攪拌混合して本発明及び比較用のネガ型感光性樹脂組成物を得た。
シリコン(Si)ウエハ基板及びシリコンウエハ上にシリコンナイトライド(SiN)を1000Åの膜厚でプラズマCVD成膜した基板の各々の上に、スピンコーターを用いて実施例1乃至4、比較例1及び比較例2の各ネガ型感光性樹脂組成物を、膜厚(乾燥後の膜厚)が20μmとなるよう塗布した後、ホットプレートを用いて120℃×2分間の条件で乾燥して各ネガ型感光性樹脂組成物層を設けた。このネガ感光性樹脂組成物層を設けた基板に、ホットプレートを用いて65℃×5分間、次いで95℃×15分間の条件でプリベークを施し、更にi線露光装置(マスクアライナー:ウシオ電機社製)を用いてパターン露光(ソフトコンタクト、i線)を施した。露光後の基板にホットプレートを用いて95℃×6分間の露光後ベーク(PEB)を施した後、プロピレングリコールモノメチルエーテルアセテートを用いて浸漬法により23℃×6分間の現像処理を行い、これに対して200℃のオーブン(窒素雰囲気下)で60分間ハードベーク処理を行い、Siウエハ基板及びSiNを製膜した基板上に硬化したネガ型感光性樹脂組成物のパターンを得た。
前記のシリコン(Si)ウエハ基板上でのパターン露光において、マスクの転写精度が最良となる露光量を最適露光量とし、それぞれのネガ型感光性樹脂組成物の感度を評価した。この評価結果で最適露光量の値が小さい組成物ほど感度が高いことを意味する。結果を下記表1に示した。
前記のネガ型感光性樹脂組成物の感度評価で得られた最適露光量によるパターン露光において、ラインアンドスペースが1:1で残渣なく解像されたレジストパターン中、基板へ密着している最も細いパターンの幅を測定してネガ型感光性樹脂組成物の解像性を評価した。結果を下記表1に示した。
評価基準
○(良好):最も細いパターン幅が10μm以下であった。
×(不良):最も細いパターン幅が10μmを超えた。
ここでいう密着力とは、シェアツールを用いてパターン側面部から力を加え、基板からパターンが剥離した時点でのシェア強度(せん断強度)である。この値が高い方が基板と樹脂組成物との密着力が高く、好ましい。具体的には、各基板上に、前記で得られた最適露光量で100μm×100μm(膜厚は20μm)のブロック状のレジストパターンを形成し、ボンディングテスター(レスカ社製)を使用し、100μmのシェアツールを用いて50μm/secの速さで基板からの高さ3μmの位置に横方向から負荷を与えた時の破壊荷重を計測した。結果を下記表1に示した。
前記のネガ型感光性樹脂組成物の感度評価で得られた最適露光量でネガ型感光性樹脂組成物の硬化物を作製し、DMA測定装置(TAインスツルメント社製 RSA-G2)を用いて、引張モード、1Hz、Ramp rate 3℃/secの条件で、175℃での弾性率を測定した。結果を下記表1に示した。
(A-1):商品名 TEPIC-VL、日産化学工業株式会社製、エポキシ当量135g/eq.(式(1)で表わされるトリアジン環を有する化合物であって、R1の全てが、R2がn-プロピレン基の式(1-1)で表される有機基の化合物)
(A-2):商品名 TEPIC-UC、日産化学工業株式会社製、エポキシ当量195g/eq.(式(1)で表わされるトリアジン環を有する化合物であって、R1の一つが、R2がメチレン基の式(1-1)で表される有機基であって、R1の残りの二つが、R5が水素原子の式(1-4)で表される有機基の化合物)
(B-1):商品名 KM-N-LCL 日本化薬株式会社製、エポキシ当量210g/eq.、軟化点85℃、重量平均分子量8000、平均繰り返し数k=4(式(2)で表わされるエポキシ樹脂)
(B-2):商品名 NC-3000H、日本化薬社株式会製、エポキシ当量285g/eq.、軟化点65℃、重量平均分子量700、平均繰り返し数p=2(式(3)で表わされるエポキシ樹脂)
(B-3):商品名 NER-7604、日本化薬株式会社製、エポキシ当量347g/eq.、軟化点71℃、重量平均分子量9000、平均繰り返し数n=4、m≦1(式(4)で表わされるエポキシ樹脂)
(B-4):商品名 jER-1007 三菱化学株式会社製、エポキシ当量2000g/eq.、重量平均分子量2900
(C-1):光酸発生剤(トリス[4-(4-アセチルフェニル)スルホニルフェニル]スルホニウムテトラキス(2,3,4,5,6-ペンタフルオロフェニル)ボレート、商品名 PAG290、BASF社製)
(D-1):商品名 EX-321L、ナガセケムテックス株式会社製、エポキシ当量140g/eq.(トリメチロールプロパントリグリシジルエーテル)
(D-2):商品名 EP-4088L 株式会社ADEKA製、エポキシ当量165g/eq.(ジシクロペンタジエンジメタノールジグリシジルエーテル)
(E):シランカップリング剤(商品名 S-510、チッソ株式会社製)
(F):レベリング剤(商品名 フタージェント222F、株式会社ネオス製)
(G):溶剤(エチレングリコールジメチルエーテル、商品名 ハイソルブMMM、東邦化学工業株式会社製)
前記の感度評価及びSi並びにSiNへの密着力評価と同様の方法で、実施例1と比較例1のネガ型感光性樹脂組成物のLT(リチウムタンタレート)基板及びAl(アルミニウム)基板への密着力を評価した。結果を下記表2に示した。尚、表2中の数値の単位は「MPa」である。
ここでいう現像後残渣とは、現像後に未露光部分に残存する、本来は現像処理により除去されなければならないネガ型感光性樹脂組成物の溶け残りのことである。
PETフィルム上に、アプリケーターを用いて実施例1、実施例3、実施例4、比較例1及び比較例2の各ネガ型感光性樹脂組成物を塗布した後、ホットプレートを用いて120℃×2分間の条件で溶剤を乾燥して厚み20μmの各ネガ型感光性樹脂組成物層(ドライフィルム)を設けた。前記で得られた各ネガ型感光性樹脂組成物層の上に、PETフィルムを、ラミネーターを用いて60℃、0.3MPaの条件で貼り付けて得られた評価用のサンプルを、温度40℃、湿度90%RHの雰囲気下に2週間さらした。
上記で得られた評価用サンプルから片面のPETフィルムを剥がして露出したネガ型感光性樹脂組成物層を、シリコン(Si)ウエハ基板上に、ラミネーターを用いて60℃、0.3MPaの条件で貼り合せた後、ホットプレート上で65℃×5分間の熱処理を行った。次に、残り片面のPETフィルムを剥がして得られたネガ型感光性樹脂組成物層付きのシリコン(Si)ウエハ基板に、プロピレングリコールモノメチルエーテルアセテートを用いて浸漬法により23℃×6分間の現像処理を行った。現像処理後のシリコン(Si)ウエハ基板の未露光部分を顕微鏡(ニコン社製 ECLIPS L150)を用いて50倍の倍率で観察し、残渣が無い場合を○(良好)、残渣が有る場合を×(不良)とした。結果を下記表3に示した。
Claims (9)
- (A)下記式(1)
(式(1)中、R1はそれぞれ独立に有機基を表す。但し、R1の少なくとも一つはグリシジル基を有する有機基又はオキセタニル基を有する有機基を表す。)
で表されるトリアジン環を有する化合物、
(B)一分子中にベンゼン骨格と二つ以上のエポキシ基を有するエポキシ当量が500g/eq.以下のエポキシ樹脂、及び
(C)光カチオン重合開始剤
を含有するネガ型感光性樹脂組成物であって、
該(B)エポキシ樹脂に対する該(A)式(1)で表される化合物の含有量が1乃至50質量%であり、且つ、
該(B)エポキシ樹脂が下記条件(i)及び(ii):
条件(i)重量平均分子量が500以上であること;及び
条件(ii)軟化点が40℃以上であること
の少なくとも一方を満たす、ネガ型感光性樹脂組成物。 - R1のいずれもが式(1-1)で表される有機基、式(1-2)で表される有機基又は式(1-3)で表される有機基である、請求項2に記載のネガ型感光性樹脂組成物。
- (B)一分子中にベンゼン骨格と二つ以上のエポキシ基を有するエポキシ当量が500g/eq.以下のエポキシ樹脂が、
下記式(2)
(式(2)中、Rはそれぞれ独立にグリシジル基又は水素原子を示し、複数存在するRのうちの少なくとも2つはグリシジル基である。kは平均値を示し、0乃至30の範囲にある実数である。)で表されるエポキシ樹脂(B-1)、
下記式(3)
(式(3)中、R6、R7及びR8は、それぞれ独立に水素原子又は炭素数1乃至4のアルキル基を示す。pは平均値を示し1乃至30の範囲にある実数である。)で表されるエポキシ樹脂(B-2)、
下記式(4)
(式(4)中、n及びmは平均値を示し、nは1乃至30の範囲にある実数であり、mは0.1乃至30の範囲にある実数であり、R9及びR10は、それぞれ独立に水素原子、炭素数1乃至4のアルキル基又はトリフルオロメチル基を示す。)で表されるエポキシ樹脂(B-3)、
下記式(5)
(式(5)中、qは平均値を示し、1乃至30の範囲にある実数である。)で表されるエポキシ樹脂(B-4)、
下記式(6)
で表されるフェノール誘導体と、エピハロヒドリンとの反応物であるエポキシ樹脂(B-5)、
1分子中に少なくとも2個以上のエポキシ基を有するエポキシ化合物と1分子中に少なくとも1個以上の水酸基と1個のカルボキシル基を有する化合物との反応物に、多塩基酸無水物を反応させることにより得られるエポキシ樹脂(B-6)、
下記式(7)
(式(7)中、sは平均値を示し、1乃至10の範囲にある実数である。)で表されるエポキシ樹脂(B-7)、
下記式(8)
(式(8)中、tは平均値を示し、0.1乃至5の範囲にある実数である。)で表されるエポキシ樹脂(B-8)、及び
下記式(9)
(式(9)中、rは平均値を示し、0.1乃至6の範囲にある実数である。)で表されるエポキシ樹脂(B-9)からなる群から選択される1種類又は2種類以上である、
請求項1乃至4のいずれか一項に記載のネガ型感光性樹脂組成物。 - 請求項1乃至5のいずれか一項に記載のネガ型感光性樹脂組成物を含むドライフィルムレジスト。
- 請求項1乃至5のいずれか一項に記載のネガ型感光性樹脂組成物又は請求項6に記載のドライフィルムレジストの硬化物。
- 請求項7に記載の硬化物を含むウエハーレベルパッケージ。
- 基板と被着体との接着層であって、請求項7に記載の硬化物を含む接着層。
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